Herbicidal 1,3-oxazin-4-one derivatives and intermediates thereto

ABSTRACT

Novel 1,3-oxazin-4-one derivatives of the formula ##STR1## wherein R 1  to R 5  are hydrocarbyl radicals which are optionally substituted, and herbicidal compositions comprising the same as active ingredients and their use in controlling the growth of weeds. The compounds can be produced by reacting substituted 1,3-dioxin-4-one derivatives and N-methylene-alkylamine.

CROSS-REFERENCE TO RELATED APPLICATION

This is a continuation-in-part of International Application No. PCT/EP94/03310, filed Oct. 6, 1994, designating the United States.

FIELD OF THE INVENTION

This invention relates to novel 1,3-oxazin-4-one derivatives which havenot been reported in any previous publication, herbicides containing thesame, and process and intermediates for preparing the same.

BACKGROUND ART

Certain types of 4H-2,3-dihydro-1,3-oxazin-4-one derivatives aredescribed in, for example, Tetrahedron Lett, (33), 2905 (1976),Heterocycles, 17, 298 (1982), Chem. Pharm. Bull., 35(5), 1871(1987).

However, the compounds described in the above publications differ fromthe compounds of this invention since none of them has a tertiary alkylor aralkyl substituent on the 3-position, and no mention is made oftheir herbicidal activity and plant growth regulator activity.

U.S. Pat. No. 5,006,157 discloses1-(1-methyl-1-phenylethyl)-3-phenyl-1,2,5,6-tetrahydropyridin-2-onederivatives and their use as herbicides. However,4H-2,3-dihydro-1,3-oxazin-4-one derivatives and their herbicidalactivity have not been described at all in the patent description. Inaddition, it has been found that the compounds disclosed in the patentdescription are not good enough in herbicidal efficacy and selectivity.

SUMMARY AND OBJECTS OF THE INVENTION

The present inventors have found that a certain type of 1,3-oxazin-4-onederivative shows herbicidal activity at low doses on various weedswithout damaging useful crops.

This invention provides 1,3-oxazin-4-one derivatives having the formula:##STR2## wherein:

R¹ is a lower alkyl radical, a lower alkenyl radical, a lower alkynylradical, an aryl radical which is unsubstituted or substituted, or anaralkyl radical which is unsubstituted or substituted;

R² is a lower haloalkyl radical, a lower hydroxyalkyl radical, a loweralkoxyalkyl radical, a lower acyloxyalkyl radical, a formyl radical, ahydroxyiminomethyl radical, a lower alkoxyiminomethyl radical, a loweracyloxyiminomethyl radical, a cyano radical, or a lower alkoxycarbonylradical;

R³ is a lower alkyl radical, an aryl radical which is unsubstituted orsubstituted, or an aralkyl radical which is unsubstituted orsubstituted; and

R⁴ and R⁵, independently, are each a lower alkyl radical, or R⁴ and R⁵,taken together with the carbon atom to which they are bonded, combine toform a 3- to 8-membered carbocyclic ring which may optionally bear oneor more alkyl radicals as substituents.

Another object of the present invention is to provide herbicidalcompositions comprising one or more compounds of formula (I) as activeingredient.

DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS

Some examples of the groups R¹, R², R³, R⁴ and R⁵ as defined in theabove formula (I) will be explained as follows:

"Lower alkyl radical" means either a straight-chained or abranched-chained alkyl radical which has 1 to 6 carbon atoms, andincludes, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, tert-pentyl,hexyl, and the like.

"Lower alkenyl radical" means an alkenyl radical which has 2 to 6 carbonatoms, and includes, for example, allyl, 2-methyl-2-propenyl, 2-butenyl,3-butenyl, 3-methyl-2-butenyl, and the like.

"Lower alkynyl radical" means an alkynyl radical which has 2 to 6 carbonatoms, and includes, for example, 2-propynyl, 1-methyl-2-propynyl,2-butynyl, 3-butynyl, and the like.

"Lower haloalkyl radical" means a haloalkyl radical which has 1 to 4carbon atoms, and includes, for example, bromomethyl, dichloromethyl,trifluoromethyl, 1-chloroethyl, 2-iodoethyl, 3-chloropropyl,2-methyl-2-chloropropyl, 2,2,2-trifluoroethyl, and the like.

"Lower hydroxyalkyl radical" means an hydroxyalkyl radical which has 1to 4 carbon atoms, and includes, for example, hydroxymethyl,2-hydroxyethyl, and the like.

"Lower alkoxyalkyl or lower acyloxyiminomethyl radical" means an alkylradical which has 1 to 4 carbon atoms and is substituted with an alkoxyradical which has 1 to 4 carbon atoms, or with an acyl radical which has2 to 5 carbon atoms, and includes, for example, methoxymethyl,ethoxymethyl, acetyloxymethyl, and the like.

"Lower alkoxyiminomethyl or lower acyloxyiminomethyl radical" means animinomethyl radical substituted with an alkoxy radical which has 1 to 4carbon atoms or with an acyl radical which has 2 to 5 carbon atoms, andincludes, for example, methoxyiminomethyl, ethoxyiminomethyl,acetyloxyiminomethyl, and the like.

"Lower alkoxycarbonyl radical" means an alkoxycarbonyl radical which has2 to 6 carbon atoms, and includes, for example, methoxycarbonyl,ethoxycarbonyl, isopropoxycarbonyl, and the like.

"Aryl radical which is unsubstituted or substituted" means an arylradical such as phenyl, naphthyl etc. which is optionally substitutedwith a halogen atom, a lower alkyl radical, a lower alkoxy radical, alower haloalkyl radical, a lower haloalkoxy radical, a nitro group,etc., and includes, for example, phenyl, 2-naphthyl, 2-fluorophenyl,2-tolyl, 3-nitrophenyl, 4-chloro-2-naphthyl, 3,5-dichlorophenyl,3,5-dimethoxyphenyl, 3,5-bis(difluoromethoxy)phenyl,3,5-dichloro-4-methylphenyl, and the like.

"Aralkyl radical which is unsubstituted or substituted" means an aralkylradical which has an "aryl radical which is unsubstituted orsubstituted" as defined above at the position of the aryl radical, andincludes, for example, benzyl, (2-chlorophenyl)methyl,1-(3-chlorophenyl)ethyl, 2-phenylethyl, 1-methyl-1-phenylethyl,1-methyl-2-phenylethyl, 1-ethyl-2-(3-trifluoromethylphenyl)ethyl,(2-difluoromethoxyphenyl)methyl, 3-phenylpropyl, and the like. The alkylportion of the aralkyl radical typically has 1 to 4 carbon atoms.

"3 to 8-Membered carbocyclic ring which may optionally bear 1 or morelower alkyl radicals as substituents" includes cyclopropane,cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane,2,2'-dimethylcyclopropane, 3,5-diethylcyclohexane, and the like, i.e.cycloalkane rings having 3 to 8 ring atoms, which are unsubstituted orsubstituted by 1 or more lower alkyl radicals.

Further, examples of a halogen atom, a lower alkoxy radical, a lowerhaloalkyl radical, a lower haloalkoxy radial, and a lower acyl radicalwill be explained as follows:

"Halogen atom" mean fluorine, chlorine, bromine or iodine.

"Lower alkoxy radical" means an alkoxy radical which has a lower alkylradical as defined above at the position of the alkyl radical, andincludes, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy,pentoxy, and the like.

"Lower haloalkyl radical" means a lower alkyl radical of which one ormore hydrogen atoms are replaced with (a) halogen atom(s) as definedabove, and includes, for example, bromomethyl, dichloromethyl,trifluoromethyl, 1-chloroethyl, 2-iodoethyl, 3-chloropropyl,2-methyl-2-chloropropyl, 2,2,2-trifluoroethyl, and the like.

"Lower haloalkoxy radical" means a haloalkoxy radical which has a lowerhaloalkyl radical as defined above at the position of alkyl radical, andincludes, for example, trifluoromethoxy, difluoromethoxy,chlorodifluoromethoxy, 2-chloroethoxy, 1,1,2,2-tetrafluoroethoxy,3-chloropropoxy, 2,2,3,3,3-pentafluoropropoxy, and the like.

"Lower acyl radical" means an acyl radical having up to 6 carbon atomsin the alkyl portion, such as acetyl, propionyl, butyryl, isobutyryl,and the like.

Any groups which have not been described above can be selected fromalready described atoms or groups by optional combination or in thewell-known usual way.

Among the compounds of this invention having formula (I) defined above,some preferable compounds are selected as follows:

R¹ is a branched alkyl radical such as isobutyl or isopropyl; or aphenyl radical, without substitution or substituted with a halogen atomor a lower alkyl radical;

R³ is phenyl or 2-naphthyl, without substitution or substituted with oneor two halogen atom(s), a lower haloalkyl radical or a lower haloalkoxyradical;

R⁴ and R⁵, independently, are each methyl.

More preferably, the compounds are selected from those of the formula:##STR3## wherein R² is as defined with formula (I) above; X is a halogenatom or a lower alkyl radical; Y is a halogen atom or a lower haloalkylradical; n is 0 or 1; and m is 0, 1 or 2.

According to the studies of the present inventors, the compounds havingthe formula (II-2) below, which can be intermediates to the compounds ofthis invention wherein R¹ is an aryl radical which may be substitutedand R² is an acetyloxymethyl radical, i.e. the compounds of the formula:##STR4## wherein R⁶ is an aryl radical which may be substituted; and thecompounds having the formula (II-1) below, which can be derived from thecompounds of formula (II-2) above, i.e. the compounds of the formula:##STR5## wherein R⁶ is an aryl radical which may be substituted and R⁷is a hydroxymethyl or a formyl radical, are novel compounds, andtherefore are included in this invention.

Thus, this invention can provide 1,3-dioxin-4-one derivatives having theformula: ##STR6## wherein R⁶ is an aryl radical which may be substitutedand R⁷ is a hydroxymethyl, an acetyloxymethyl or a formyl radical.

In formula (II) above:

"R⁶ is an aryl radical which may be substituted" means an aryl radicalsuch as phenyl or naphthyl, or such an aryl radical which is substitutedwith a halogen atom, a lower alkyl radical, a lower alkoxy radical, alower haloalkyl radical, a nitro group, etc. From these substitutions, aphenyl radical substituted at the 2-position can be selected preferably.

In formula (II) above, examples of groups defined by R⁶ are exactly thesame as described previously.

Examples of specific compounds of this invention having formula (I) areshown in Table 1 below, and those having formula (II) are shown in Table2 below. ##STR7##

                                      TABLE 1                                     __________________________________________________________________________    Compd.                                                                            R.sup.1        R.sup.3                                                    No.    (X).sub.n                                                                          R.sup.2   (Y).sub.m                                                                           R.sup.4                                                                             R.sup.5                                     __________________________________________________________________________    1   (A)                                                                              --   CH.sub.2 F                                                                           (a)                                                                              --    Me    Me                                          2   (A)                                                                              --   CH.sub.2 F                                                                           (a)                                                                              3-F   Me    Me                                          3   (A)                                                                              --   CH.sub.2 F                                                                           (a)                                                                              3-Cl  Me    Me                                          4   (A)                                                                              --   CH.sub.2 F                                                                           (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          5   (A)                                                                              --   CH.sub.2 F                                                                           (a)                                                                              3-Me  Me    Me                                          6   (A)                                                                              --   CH.sub.2 F                                                                           (a)                                                                              3-CF.sub.3                                                                          Me    Me                                          7   (A)                                                                              2-F  CH.sub.2 F                                                                           (a)                                                                              --    Me    Me                                          8   (A)                                                                              2-F  CH.sub.2 F                                                                           (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          9   (A)                                                                              2-Cl CH.sub.2 F                                                                           (a)                                                                              --    Me    Me                                          10  (A)                                                                              2-Cl CH.sub.2 F                                                                           (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          11  (A)                                                                              2-Me CH.sub.2 F                                                                           (a)                                                                              --    Me    Me                                          12  (A)                                                                              3-Me CH.sub.2 F                                                                           (a)                                                                              --    Me    Me                                          13  (A)                                                                              2-CF.sub.3                                                                         CH.sub.2 F                                                                           (a)                                                                              --    Me    Me                                          14  (A)                                                                              --   CH.sub.2 F                                                                           (b)                                                                              --    Me    Me                                          15  (A)                                                                              --   CH.sub.2 F                                                                           (b)                                                                              4-Cl  Me    Me                                          16  (A)                                                                              --   CH.sub.2 F                                                                           (c)                                                                              --    Me    Me                                          17  (B)                                                                              --   CH.sub.2 F                                                                           (a)                                                                              --    Me    Me                                          18  (B)                                                                              --   CH.sub.2 F                                                                           (a)                                                                              3-Cl  Me    Me                                          19  (B)                                                                              --   CH.sub.2 F                                                                           (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          20  (C)                                                                              --   CH.sub.2 F                                                                           (a)                                                                              --    Me    Me                                          21  (C)                                                                              --   CH.sub.2 F                                                                           (a)                                                                              3-Cl  Me    Me                                          22  (A)                                                                              --   CH.sub.2 F                                                                           Me       Me    Me                                          23  (A)                                                                              --   CH.sub.2 F                                                                           Et       Me    Me                                          24  (A)                                                                              --   CH.sub.2 F                                                                           Pr       Me    Me                                          25  (A)                                                                              --   CH.sub.2 F                                                                           tBu      Me    Me                                          26  Me      CH.sub.2 F                                                                           (a)                                                                              --    Me    Me                                          27  Me      CH.sub.2 F                                                                           (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          28  Et      CH.sub.2 F                                                                           (a)                                                                              --    Me    Me                                          29  Et      CH.sub.2 F                                                                           (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          30  iPr     CH.sub.2 F                                                                           (a)                                                                              --    Me    Me                                          31  iPr     CH.sub.2 F                                                                           (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          32  Bu      CH.sub.2 F                                                                           (a)                                                                              --    Me    Me                                          33  Bu      CH.sub.2 F                                                                           (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          34  (A)                                                                              --   CHF.sub.2                                                                            (a)                                                                              --    Me    Me                                          35  (A)                                                                              --   CHF.sub.2                                                                            (a)                                                                              3-Cl  Me    Me                                          36  (A)                                                                              --   CHF.sub.2                                                                            (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          37  (A)                                                                              2-F  CHF.sub.2                                                                            (a)                                                                              --    Me    Me                                          38  (A)                                                                              2-Cl CHF.sub.2                                                                            (a)                                                                              --    Me    Me                                          39  (A)                                                                              2-Me CHF.sub.2                                                                            (a)                                                                              --    Me    Me                                          40  (A)                                                                              --   CHF.sub.2                                                                            (b)                                                                              --    Me    Me                                          41  (A)                                                                              --   CHF.sub.2                                                                            (c)                                                                              --    Me    Me                                          42  (B)                                                                              --   CHF.sub.2                                                                            (a)                                                                              --    Me    Me                                          43  (C)                                                                              --   CHF.sub.2                                                                            (a)                                                                              --    Me    Me                                          44  (A)                                                                              --   CHF.sub.2                                                                            Me       Me    Me                                          45  (A)                                                                              --   CHF.sub.2                                                                            Et       Me    Me                                          46  Me      CHF.sub.2                                                                            (a)                                                                              --    Me    Me                                          47  Me      CHF.sub.2                                                                            (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          48  (A)                                                                              --   CF.sub.3                                                                             (a)                                                                              --    Me    Me                                          49  (A)                                                                              --   CF.sub.3                                                                             (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          50  (A)                                                                              --   CF.sub.3                                                                             (b)                                                                              --    Me    Me                                          51  (A)                                                                              --   CF.sub.3                                                                             (c)                                                                              --    Me    Me                                          52  (A)                                                                              --   CF.sub.3                                                                             Me       Me    Me                                          53  (A)                                                                              --   CH.sub.2 OH                                                                          (a)                                                                              --    Me    Me                                          54  (A)                                                                              --   CH.sub.2 OH                                                                          (a)                                                                              3-Cl  Me    Me                                          55  (A)                                                                              --   CH.sub.2 OH                                                                          (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          56  (A)                                                                              --   CH.sub.2 OH                                                                          (b)                                                                              --    Me    Me                                          57  (A)                                                                              --   CH.sub.2 OH                                                                          (c)                                                                              --    Me    Me                                          58  (B)                                                                              --   CH.sub.2 OH                                                                          (a)                                                                              --    Me    Me                                          59  (C)                                                                              --   CH.sub.2 OH                                                                          (a)                                                                              --    Me    Me                                          60  (A)                                                                              --   CH.sub.2 OH                                                                          Me       Me    Me                                          61  (A)                                                                              --   CH.sub.2 OH                                                                          Et       Me    Me                                          62  Me      CH.sub.2 OH                                                                          (a)                                                                              --    Me    Me                                          63  Et      CH.sub.2 OH                                                                          (a)                                                                              --    Me    Me                                          64  iPr     CH.sub.2 OH                                                                          (a)                                                                              --    Me    Me                                          65  Bu      CH.sub.2 OH                                                                          (a)                                                                              --    Me    Me                                          66  (A)                                                                              --   CH.sub.2 OAc                                                                         (a)                                                                              --    Me    Me                                          67  (A)                                                                              --   CH.sub.2 OAc                                                                         (a)                                                                              3-F   Me    Me                                          68  (A)                                                                              --   CH.sub.2 OAc                                                                         (a)                                                                              3-Cl  Me    Me                                          69  (A)                                                                              --   CH.sub.2 OAc                                                                         (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          70  (A)                                                                              --   CH.sub.2 OAc                                                                         (a)                                                                              3-Me  Me    Me                                          71  (A)                                                                              --   CH.sub.2 OAc                                                                         (a)                                                                              3-CF.sub.3                                                                          Me    Me                                          72  (A)                                                                              --   CH.sub.2 OAc                                                                         (a)                                                                              3-OMe Me    Me                                          73  (A)                                                                              2-F  CH.sub.2 OAc                                                                         (a)                                                                              --    Me    Me                                          74  (A)                                                                              2-F  CH.sub.2 OAc                                                                         (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          75  (A)                                                                              2-Cl CH.sub.2 OAc                                                                         (a)                                                                              --    Me    Me                                          76  (A)                                                                              2-Cl CH.sub.2 OAc                                                                         (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          77  (A)                                                                              3-Cl CH.sub.2 OAc                                                                         (a)                                                                              --    Me    Me                                          78  (A)                                                                              3-Cl CH.sub.2 OAc                                                                         (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          79  (A)                                                                              2-Me CH.sub.2 OAc                                                                         (a)                                                                              --    Me    Me                                          80  (A)                                                                              2-Me CH.sub.2 OAc                                                                         (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          81  (A)                                                                              3-Me CH.sub.2 OAc                                                                         (a)                                                                              --    Me    Me                                          82  (A)                                                                              3-Me CH.sub.2 OAc                                                                         (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          83  (A)                                                                              --   CH.sub.2 OAc                                                                         (b)                                                                              --    Me    Me                                          84  (A)                                                                              --   CH.sub.2 OAc                                                                         (b)                                                                              4-Cl  Me    Me                                          85  (A)                                                                              --   CH.sub.2 OAc                                                                         (c)                                                                              --    Me    Me                                          86  (A)                                                                              --   CH.sub.2 OAc                                                                         (c)                                                                              3-Cl  Me    Me                                          87  (A)                                                                              --   CH.sub.2 OAc                                                                         (d)                                                                              --    Me    Me                                          88  (A)                                                                              --   CH.sub.2 OAc                                                                         (d)                                                                              2-Cl  Me    Me                                          89  (A)                                                                              --   CH.sub.2 OAc                                                                         (d)                                                                              2-Me  Me    Me                                          90  (B)                                                                              --   CH.sub.2 OAc                                                                         (a)                                                                              --    Me    Me                                          91  (B)                                                                              --   CH.sub.2 OAc                                                                         (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          92  (C)                                                                              --   CH.sub.2 OAc                                                                         (a)                                                                              --    Me    Me                                          93  (C)                                                                              --   CH.sub.2 OAc                                                                         (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          94  (E)                                                                              --   CH.sub.2 OAc                                                                         (a)                                                                              --    Me    Me                                          95  (E)                                                                              --   CH.sub.2 OAc                                                                         (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          96  (F)                                                                              --   CH.sub.2 OAc                                                                         (a)                                                                              --    Me    Me                                          97  (F)                                                                              --   CH.sub.2 OAc                                                                         (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          98  (A)                                                                              --   CH.sub.2 OAc                                                                         Me       Me    Me                                          99  (A)                                                                              --   CH.sub.2 OAc                                                                         Et       Me    Me                                          100 (A)                                                                              --   CH.sub.2 OAc                                                                         Pr       Me    Me                                          101 (A)                                                                              --   CH.sub.2 OAc                                                                         iPr      Me    Me                                          102 (A)                                                                              --   CH.sub.2 OAc                                                                         Bu       Me    Me                                          103 (A)                                                                              --   CH.sub.2 OAc                                                                         tBu      Me    Me                                          104 Me      CH.sub.2 OAc                                                                         (a)                                                                              --    Me    Me                                          105 Me      CH.sub.2 OAc                                                                         (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          106 Et      CH.sub.2 OAc                                                                         (a)                                                                              --    Me    Me                                          107 Et      CH.sub.2 OAc                                                                         (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          108 CHCH.sub.2                                                                            CH.sub.2 OAc                                                                         (a)                                                                              --    Me    Me                                          109 CHCH.sub.2                                                                            CH.sub.2 OAc                                                                         (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          110 CH.sub.2 CHCH.sub.2                                                                   CH.sub.2 OAc                                                                         (a)                                                                              --    Me    Me                                          111 CH.sub.2 CHCH.sub.2                                                                   CH.sub.2 OAc                                                                         (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          112 CCH     CH.sub.2 OAc                                                                         (a)                                                                              --    Me    Me                                          113 CCH     CH.sub.2 OAc                                                                         (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          114 (A)                                                                              --   CH.sub.2 OAc                                                                         (a)                                                                              --    Me    Me                                          115 (A)                                                                              --   CH.sub.2 OAc                                                                         (a)                                                                              3-Cl  Me    Me                                          116 (A)                                                                              --   CH.sub.2 OAc                                                                         (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          117 (A)                                                                              --   CH.sub.2 OAc                                                                         (b)                                                                              --    Me    Me                                          118 (A)                                                                              --   CH.sub.2 OAc                                                                         (c)                                                                              --    Me    Me                                          119 (A)                                                                              --   CH.sub.2 OAc                                                                         Me       Me    Me                                          120 (A)                                                                              --   CH.sub.2 OAc                                                                         Et       Me    Me                                          121 (A)                                                                              --   CHO    (a)                                                                              --    Me    Me                                          122 (A)                                                                              --   CHO    (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          123 (A)                                                                              --   CHO    (b)                                                                              --    Me    Me                                          124 (A)                                                                              --   CHO    (c)                                                                              --    Me    Me                                          125 (A)                                                                              --   CHO    (d)                                                                              --    Me    Me                                          126 (B)                                                                              --   CHO    (a)                                                                              --    Me    Me                                          127 (B)                                                                              --   CHO    (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          128 (C)                                                                              --   CHO    (a)                                                                              --    Me    Me                                          129 (A)                                                                              --   CHO    Me       Me    Me                                          130 (A)                                                                              --   CHO    Et       Me    Me                                          131 (A)                                                                              --   CHO    Pr       Me    Me                                          132 Me      CHO    (a)                                                                              --    Me    Me                                          133 Et      CHO    (a)                                                                              --    Me    Me                                          134 (A)                                                                              --   CHNOH  (a)                                                                              --    Me    Me                                          135 (A)                                                                              --   CHNOH  (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          136 (A)                                                                              --   CHNOH  (b)                                                                              --    Me    Me                                          137 (A)                                                                              --   CHNOH  (c)                                                                              --    Me    Me                                          138 (B)                                                                              --   CHNOH  (a)                                                                              --    Me    Me                                          139 (C)                                                                              --   CHNOH  (a)                                                                              --    Me    Me                                          140 (A)                                                                              --   CHNOH  Me       Me    Me                                          141 (A)                                                                              --   CHNOH  Et       Me    Me                                          142 (A)                                                                              --   CHNOH  Pr       Me    Me                                          143 (A)                                                                              --   CHNOH  iPr      Me    Me                                          144 Me      CHNOH  (a)                                                                              --    Me    Me                                          145 (A)                                                                              --   CHNOAc (a)                                                                              --    Me    Me                                          146 (A)                                                                              --   CHNOAc (a)                                                                              3-Cl  Me    Me                                          147 (A)                                                                              --   CHNOAc (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          148 (A)                                                                              2-F  CHNOAc (a)                                                                              --    Me    Me                                          149 (A)                                                                              2-F  CHNOAc (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          150 (A)                                                                              2-Cl CHNOAc (a)                                                                              --    Me    Me                                          151 (A)                                                                              2-Cl CHNOAc (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          152 (A)                                                                              2-Me CHNOAc (a)                                                                              --    Me    Me                                          153 (A)                                                                              2-Me CHNOAc (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          154 (A)                                                                              --   CHNOAc (b)                                                                              --    Me    Me                                          155 (A)                                                                              --   CHNOAc (c)                                                                              --    Me    Me                                          156 (A)                                                                              --   CHNOAc Me       Me    Me                                          157 (A)                                                                              --   CHNOAc Et       Me    Me                                          158 (A)                                                                              --   CHNOMe (a)                                                                              --    Me    Me                                          159 (A)                                                                              --   CHNOMe (a)                                                                              3-Cl  Me    Me                                          160 (A)                                                                              --   CHNOMe (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          161 (A)                                                                              --   CHNOMe (b)                                                                              --    Me    Me                                          162 (A)                                                                              --   CHNOMe Me       Me    Me                                          163 (A)                                                                              --   CHNOMe Et       Me    Me                                          164 (A)                                                                              --   CN     (a)                                                                              --    Me    Me                                          165 (A)                                                                              --   CN     (a)                                                                              3-F   Me    Me                                          166 (A)                                                                              --   CN     (a)                                                                              3-Cl  Me    Me                                          167 (A)                                                                              --   CN     (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          168 (A)                                                                              --   CN     (a)                                                                              3-Me  Me    Me                                          169 (A)                                                                              --   CN     (a)                                                                              3-CF.sub.3                                                                          Me    Me                                          170 (A)                                                                              --   CN     (b)                                                                              --    Me    Me                                          171 (A)                                                                              --   CN     (c)                                                                              --    Me    Me                                          172 (B)                                                                              --   CN     (a)                                                                              --    Me    Me                                          173 (B)                                                                              --   CN     (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          174 (A)                                                                              --   CN     Me       Me    Me                                          175 (A)                                                                              --   CN     Et       Me    Me                                          176 (A)                                                                              --   COOMe  (a)                                                                              --    Me    Me                                          177 (A)                                                                              --   COOMe  (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          178 (A)                                                                              --   COOMe  (b)                                                                              --    Me    Me                                          179 (A)                                                                              --   COOMe  Me       Me    Me                                          180 (A)                                                                              --   COOMe  Et       Me    Me                                          181 (A)                                                                              --   COOEt  (a)                                                                              --    Me    Me                                          182 (A)                                                                              --   COOEt  (a)                                                                              3-Cl, 5-Cl                                                                          Me    Me                                          183 (A)                                                                              --   COOEt  (b)                                                                              --    Me    Me                                          184 (A)                                                                              --   COOEt  Me       Me    Me                                          185 (A)                                                                              --   COOEt  Et       Me    Me                                          186 (A)                                                                              --   CH.sub.2 F                                                                           (a)                                                                              --    Me    Et                                          187 (A)                                                                              --   CHF.sub.2                                                                            (a)                                                                              --    Me    Et                                          188 (A)                                                                              --   CF.sub.3                                                                             (a)                                                                              --    Me    Et                                          189 (A)                                                                              --   CH.sub.2 OH                                                                          (a)                                                                              --    Me    Et                                          190 (A)                                                                              --   CH.sub.2 OH                                                                          (a)                                                                              3-Cl  Me    Et                                          191 (A)                                                                              --   CH.sub.2 OH                                                                          (a)                                                                              3-Cl, 5-Cl                                                                          Me    Et                                          192 (A)                                                                              --   CH.sub.2 OAc                                                                         (a)                                                                              --    Me    Et                                          193 (A)                                                                              --   CH.sub.2 OMe                                                                         (a)                                                                              --    Me    Et                                          194 (A)                                                                              --   CHO    (a)                                                                              --    Me    Et                                          195 (A)                                                                              --   CHO    (a)                                                                              3-Cl  Me    Et                                          196 (A)                                                                              --   CHO    (a)                                                                              3-Cl, 5-Cl                                                                          Me    Et                                          197 (A)                                                                              --   CHNOH  (a)                                                                              --    Me    Et                                          198 (A)                                                                              --   CHNOAc (a)                                                                              --    Me    Et                                          199 (A)                                                                              --   CHNOMe (a)                                                                              --    Me    Et                                          200 (A)                                                                              --   CN     (a)                                                                              --    Me    Et                                          201 (A)                                                                              --   COOMe  (a)                                                                              --    Me    Et                                          202 (A)                                                                              --   CH.sub.2 F                                                                           (a)                                                                              --    CH.sub.2 CH.sub.2                                 203 (A)                                                                              --   CHF.sub.2                                                                            (a)                                                                              --    CH.sub.2 CH.sub.2                                 204 (A)                                                                              --   CF.sub.3                                                                             (a)                                                                              --    CH.sub.2 CH.sub.2                                 205 (A)                                                                              --   CH.sub.2 OH                                                                          (a)                                                                              --    CH.sub.2 CH.sub.2                                 206 (A)                                                                              --   CH.sub.2 OAc                                                                         (a)                                                                              --    CH.sub.2 CH.sub.2                                 207 (A)                                                                              --   CHO    (a)                                                                              --    CH.sub.2 CH.sub.2                                 208 (A)                                                                              --   CN     (a)                                                                              --    CH.sub.2 CH.sub.2                                 209 (A)                                                                              --   CH.sub.2 F                                                                           (a)                                                                              --    CH.sub.2 CH.sub.2 CH.sub.2                        210 (A)                                                                              --   CHF.sub.2                                                                            (a)                                                                              --    CH.sub.2 CH.sub.2 CH.sub.2                        211 (A)                                                                              --   CF.sub.3                                                                             (a)                                                                              --    CH.sub.2 CH.sub.2 CH.sub.2                        212 (A)                                                                              --   CH.sub.2 OH                                                                          (a)                                                                              --    CH.sub.2 CH.sub.2 CH.sub.2                        213 (A)                                                                              --   CH.sub.2 OAc                                                                         (a)                                                                              --    CH.sub.2 CH.sub.2 CH.sub.2                        214 (A)                                                                              --   CHO    (a)                                                                              --    CH.sub.2 CH.sub.2 CH.sub.2                        215 (A)                                                                              --   CN     (a)                                                                              --    CH.sub.2 CH.sub.2 CH.sub.2                        216 (A)                                                                              --   CH.sub.2 F                                                                           (a)                                                                              --    CH.sub.2 (CH.sub.2).sub.2 CH.sub.2                217 (A)                                                                              --   CHF.sub.2                                                                            (a)                                                                              --    CH.sub.2 (CH.sub.2).sub.2 CH.sub.2                218 (A)                                                                              --   CF.sub.3                                                                             (a)                                                                              --    CH.sub.2 (CH.sub.2).sub.2 CH.sub.2                219 (A)                                                                              --   CH.sub.2 OH                                                                          (a)                                                                              --    CH.sub.2 (CH.sub.2).sub.2 CH.sub.2                220 (A)                                                                              --   CH.sub.2 OH                                                                          (a)                                                                              3-Cl  CH.sub.2 (CH.sub.2).sub.2 CH.sub.2                221 (A)                                                                              --   CH.sub.2 OAc                                                                         (a)                                                                              --    CH.sub.2 (CH.sub.2).sub.2 CH.sub.2                222 (A)                                                                              --   CH.sub.2 OAc                                                                         (a)                                                                              3-Cl  CH.sub.2 (CH.sub.2).sub.2 CH.sub.2                223 (A)                                                                              --   CHO    (a)                                                                              --    CH.sub.2 (CH.sub.2).sub.2 CH.sub.2                224 (A)                                                                              --   CHO    (a)                                                                              3-Cl  CH.sub.2 (CH.sub.2).sub.2 CH.sub.2                225 (A)                                                                              --   CN     (a)                                                                              --    CH.sub.2 (CH.sub.2).sub.2 CH.sub.2                226 (A)                                                                              --   CH.sub.2 F                                                                           (a)                                                                              --    CH.sub.2 (CH.sub.2).sub.3 CH.sub.2                227 (A)                                                                              --   CHF.sub.2                                                                            (a)                                                                              --    CH.sub.2 (CH.sub.2).sub.3 CH.sub.2                228 (A)                                                                              --   CF.sub.3                                                                             (a)                                                                              --    CH.sub.2 (CH.sub.2).sub.3 CH.sub.2                229 (A)                                                                              --   CH.sub.2 OH                                                                          (a)                                                                              --    CH.sub.2 (CH.sub.2).sub.3 CH.sub.2                230 (A)                                                                              --   CH.sub.2 OH                                                                          (a)                                                                              3-Cl  CH.sub.2 (CH.sub.2).sub.3 CH.sub.2                231 (A)                                                                              --   CH.sub.2 OAc                                                                         (a)                                                                              --    CH.sub.2 (CH.sub.2).sub.3 CH.sub.2                232 (A)                                                                              --   CH.sub.2 OAc                                                                         (a)                                                                              3-Cl  CH.sub.2 (CH.sub.2).sub.3 CH.sub.2                233 (A)                                                                              --   CHO    (a)                                                                              --    CH.sub.2 (CH.sub.2).sub.3 CH.sub.2                234 (A)                                                                              --   CHO    (a)                                                                              3-Cl  CH.sub.2 (CH.sub.2).sub.3 CH.sub.2                235 (A)                                                                              --   CN     (a)                                                                              --    CH.sub.2 (CH.sub.2).sub.3 CH.sub.2                __________________________________________________________________________

                  TABLE 2                                                         ______________________________________                                         ##STR8##                                                                     Compd.                                                                        No.       R.sup.6     (X).sub.n R.sup.7                                       ______________________________________                                        236       (A)         --        CH.sub.2 OH                                   237       (A)         2-F       CH.sub.2 OH                                   238       (A)         2-Cl      CH.sub.2 OH                                   239       (A)         2-Me      CH.sub.2 OH                                   240       (B)         --        CH.sub.2 OH                                   241       (A)         --        CH.sub.2 OAc                                  242       (A)         2-F       CH.sub.2 OAc                                  243       (A)         2-Cl      CH.sub.2 OAc                                  244       (A)         2-Me      CH.sub.2 OAc                                  245       (B)         --        CH.sub.2 OAc                                  246       (A)         --        CHO                                           247       (A)         2-F       CHO                                           ______________________________________                                    

The compounds of the present invention having formula (I) can beprepared, for example, by the following process; however, this inventionis not limited by this example.

Method A: ##STR9##

The compounds of formula (I) of this invention can thus be prepared byreacting the compounds of formula (II') with the compounds of formula(III) in a suitable solvent or without solvent.

The reaction temperature can be set optionally between 90° and 160° C.,or in the range of the boiling point of the solvent used.

Insofar as concerns the solvent, there is no limitation thereon; anysolvent may be used which is substantially inert. However, it ispreferred from the viewpoint of the reaction temperature to use solventswith high boiling points such as toluene, xylene, mesitylene and thelike.

Reaction time may vary depending upon the reaction conditions used;typically, the reaction may be completed in 1 to 120 minutes.

Further, there is no strict limitation for the proportions of thecompounds of formula (III) to the compounds of formula (II'); however,it is convenient to use the compounds of formula (III) in an amountwithin the range of usually 0.5 to 2 moles, and particularly 0.9 to 1.1moles, per mole of the compounds of formula (II').

Separation and purification of the compounds of formula (I) produced inthis manner may be carried out by methods known per se, such asrecrystallization and column chromatography.

The compounds of formula (II') which are used as starting materials inthe above chemical reaction can be prepared by the same productionmethods as the compounds of formula (II) of this invention. Theproduction methods for the compounds of formula (II) will be describedlater in detail.

The compounds of formula (III) which are used as starting materials forthe above chemical reaction can be prepared by methods known per se, forexample, the methods described in U.S. Pat. No. 2,582,128, or relatedmethods.

It has been found that the compounds of formula (III) are mostly inequilibrium states with trimers represented by the formula below ataround room temperature, and sometimes exist as mixtures therewith, orcan exist in some cases as trimers alone, although this differs somewhataccording to different substitutions. The equilibrium can berepresented: ##STR10## wherein R³, R⁴ and R⁵ are as defined with formula(I) hereinabove.

Therefore, although the compounds of formula (III) include not onlymonomers but also mixtures of the above-described trimers and themonomers, they are represented herein by the structures and names of themonomers for the sake of simplicity.

Method B:

As substitutes for the compounds of formula (II') in the above process,the compounds of the formula: ##STR11## wherein R¹ and R² are as definedabove with formula (I) and R is a lower alkyl radical, can be used.

More specifically, the compounds of formula (I) of this invention can beprepared by the following process: ##STR12## wherein R¹, R², R³, R⁴ andR⁵ are as defined with formula (I) described previously; and R is alower alkyl radical.

The compounds of formula (I) of this invention can thus be prepared byreacting the compounds of formula (IV) with the compounds of formula(III) in a suitable solvent or without solvent. The details of thisreaction are exactly the same as the production of the compounds offormula (I) by Method A, except that the compounds of formula (II') inMethod A are replaced with the compounds of formula (IV).

The compounds of formula (IV) can be prepared by methods known per se ormethods related to those.

Method C:

In addition, there is another method for preparing the compounds offormula (I) of this invention. An acetyloxymethyl radical of thecompounds of this invention having formula (I-2) is converted step bystep as seen in the Method C herebelow: ##STR13## wherein R¹, R³, R⁴ andR⁵ are as defined with formula (I) hereinabove, A¹ is a lower alkylradical and A² is a lower alkyl or lower acyl radical, by proceduressuch as are illustrated in the synthetic Example set forth below.

The compounds of formula (I-2) can be prepared, for example, by Method Afrom the compounds of formula (II-2) of this invention describedhereinabove.

Next, the production methods for the compounds of formula (II) will beexplained. However, this invention is not limited by these productionmethods.

Among the compounds of formula (II), the compounds of formula (II-2) canbe prepared, for example, by the following process: ##STR14## wherein R⁶is an aryl radical which may be substituted, Z is a halogen atom and Mis an alkali metal.

The compounds of formula (VI) can be prepared by reacting the compoundsof formula (V) with a halogenation reagent in a suitable solvent orwithout solvent. The reaction temperature can be set optionally in therange from ice cooling temperature to the boiling point of the solventused.

Although the reaction time may vary depending upon the other reactionconditions, usually the reaction can be completed in 1 to 24 hours.

As the halogenation reagent, for example, chlorine, bromine,N-chlorosuccinimide, or N-bromosuccinimide can be used.

As solvent in case of reaction in a solvent, there is no limitationthereon; any solvent may be used which is substantially inert. Forexample, carbon tetrachloride, chloroform or acetic acid can be used.

There is no strict limitation for the proportions of the halogenationreagent to the compounds of formula (V); however, it is convenient touse the halogenation reagent in an amount within 0.5 to 2 moles per moleof the compounds of formula (V).

It is also possible to accelerate the chemical reaction by addingcatalysts or by lighting.

The product of formula (VI) can be isolated from the reaction mixtureand can be purified by methods known per se, such as recrystallizationand column chromatography.

Then, the compounds of formula (II-2) of this invention can be preparedby reacting the compounds of formula (VI) produced above with an alkalimetal salt of acetic acid, such as sodium acetate, in a suitablesolvent. The reaction temperature can be set optionally in the rangefrom room temperature to the boiling point of the solvent used.

Although the reaction time may vary depending on the other reactionconditions, usually the reaction can be completed in 1 to 12 hours.

As solvent, there is no limitation so long as it is substantially inertduring the chemical reaction described above.

Further, there is no strict limitation for the proportion of alkalimetal salt of acetic acid to the compounds of formula (VI), and it isconvenient to use the alkali metal salt of acetic acid in an amountwithin the range of 0.5 to 5 moles per mole of the compounds of formula(VI).

The products of formula (II-2) can be isolated from the reaction mixtureby methods known per se, and can be purified by recrystallization andcolumn chromatography.

The compounds of formula (V) used as starting materials can be preparedby already known methods, for example as published in Chem. Pharm.Bull., 31 (6), 1895 (1983).

Among the compounds of formula (II) described hereinabove, the compoundsof formula (II-1) above can be prepared by converting, step by step, theacetyloxymethyl group of the compounds of formula (II-2) to thehydroxymethyl group and then to the formyl group by already knownmethods, i.e. according to the scheme: ##STR15## wherein R⁶ is an arylradical which may be substituted.

The compounds of formula (II-1-a) can be prepared from the compounds offormula (II-2) by reacting in a suitable solvent or without solvent, forexample, hydrolysis in the presence of base or ester-exchange with alower alcohol.

Further, the compounds of formula (II-1-b) can be prepared from thecompounds of formula (II-1-a), for example, by reacting with anoxidizing reagent in a suitable solvent and with a catalyst, if needed.

As oxidizing reagent, for example, chromium oxide, chromate, dichromate,manganese dioxide, oxygen or dimethylsulfoxide can be used.

The novel compounds of formula (I) of the present invention haveherbicidal activity; therefore, new herbicidal compositions comprisingthe compounds of formula (I) as active ingredients are also provided bythe present invention.

When the compounds of this invention are used as herbicides, they aremixed with carriers or diluents, as well as, when desired, variousadditives and auxiliaries, by methods known per se and formed into aformulate which is acceptable for use as agricultural compositions, forinstance, dusts, granules, wettable powders, emulsifiable concentrates,soluble powders, flowable compositions, etc. They can be used asmixtures or in combination with other agricultural chemicals, forexample, fungicides, insecticides, acaricides, herbicides, plant growthregulators, fertilizers, and/or soil conditioners.

In particular, the use of the compounds of this invention as mixtureswith other herbicides can lead not only to reduction in dose, and/orreduction in manpower, but also to broadening of the herbicidal spectrumattributable to cooperative activities and further improved effectsattributable to synergistic activities by both agents.

The carriers or diluents used for formulation herein include generallysolid or liquid carriers or diluents.

Examples of appropriate solid carriers or diluents include claysrepresented by kaolinites, montmorillonites, illites, polygroskites,etc., more specifically pyrophyllite, attapulgite, sepiolite, kaolinite,bentonite, vermiculite, mica, talc, etc.; and other inorganic substancessuch as gypsum, calcium carbonate, dolomite, diatomaceous earth,magnesium lime, phosphorus lime, zeolite, silicic anhydride, syntheticcalcium silicate, etc.; organic substances of vegetable origin, such assoybean flour, tobacco flour, walnut flour, wheat flour, sawdust,starch, crystalline cellulose, etc.; synthetic or natural polymers suchas coumarone resin, petroleum resin, alkyd resin, polyvinyl chloride,polyalkylene glycol, ketone resin, ester gum, copal gum, dammar gum,etc.; waxes such as carnauba wax, beeswax, etc.; or urea and the like.

Examples of suitable liquid carriers include paraffin or naphthenehydrocarbons such as kerosene, mineral oil, spindle oil, white oil,etc.; aromatic hydrocarbons such as xylene, ethylbenzene, cumene,methylnaphthalene, etc.; chlorinated hydrocarbons such astrichloroethylene, monochlorobenzene, o-chlorotoluene, etc.; ethers suchas dioxane, tetrahydrofuran, etc.; ketones such as acetone, methyl ethylketone, diisobutyl ketone, cyclohexanone, acetophenone, isophorone,etc.; esters such as ethyl acetate, amyl acetate, ethylene glycolacetate, diethylene glycol acetate, dibutyl maleate, diethyl succinate,etc.; alcohols such as methanol, n-hexanol, ethylene glycol, diethyleneglycol, cyclohexanol, benzyl alcohol, etc.; ether alcohols such asethylene glycol ethyl ether, diethylene glycol butyl ether, etc.; polarsolvents such as dimethylformamide, dimethylsulfoxide, etc.; and water.

In addition, surfactants and other auxiliary agents may be used forvarious purposes such as emulsification, dispersion, humidification,spreading, dilation, combination, destruction control, stabilization,improvement of flowability, prevention of corrosion, prevention offreezing, etc., of the compounds of the invention.

As the surfactant, there may be used one of any types among nonionic,anionic, cationic and amphoteric surfactants. Usually, nonionic and/oranionic surfactants are used.

As suitable nonionic surfactants there can be mentioned, for example,additive polymerization products of ethylene oxide with higher alcoholssuch as lauryl alcohol, stearyl alcohol, oleyl alcohol, etc.; additivepolymerization products of ethylene oxide with alkylnaphthols such asbutylnaphthol, octylnaphthol, etc.; additive polymerization products ofethylene oxide with higher fatty acids such as palmitic acid, stearicacid, oleic acid, etc.; esters of higher fatty acids and polyhydricalcohols such as sorbitan, and additive polymerization products ofethylene oxide therewith; etc.

As suitable anionic surfactants there can be mentioned, for example,salts of alkyl sulfuric acid ester such as sodium laurylsulfate, aminesalts of sulfuric acid ester of oleyl alcohol, etc., alkyl sulfonatesalts such as sodium dioctyl sulfosuccinate, sodium2-ethylhexenesulfonate, etc., arylsulfonate salts such as sodiumisopropyl naphthalenesulfonate, sodium methylenebisnaphthalenesulfonate,etc., and the like.

Further, for the purpose of improving the properties of theformulations, i.e. to enhance the effects and so forth, the herbicidesof this invention may be used in combination with polymers and otherauxiliary agents such as casein, gelatin, albumin, glue, sodiumalginate, carboxymethylcellulose, methylcellulose,hydroxyethylcellulose, poly(vinyl alcohol), etc.

The above-described carriers or various auxiliary agents are used singlyor in combination with others depending upon the purposes of thecompositions, taking into consideration, for instance, the forms of theformulation, the conditions of application, etc.

The contents of active ingredients in the various formulations of thisinvention thus prepared may vary widely depending upon the form of theformulation; however, a suitable content of active ingredient isgenerally within the range of 0.1 to 99% by weight, and preferablywithin the range of 1 to 80% by weight.

In the case of a wettable powder, the formulate prepared generallycontains active ingredient compounds in the range of about 25 to 90%,with the remaining ingredients being solid carriers and dispersionwetting agents. If necessary, colloid protection agents, defoamingagents, and so forth may be added thereto.

In the case of granules, the formulate contains active ingredientcompounds usually in the range of about 1 to 35% by weight, with theremainder being solid carriers and surfactants. The active ingredientcompounds may be mixed with solid carriers uniformly, or fixed to oradsorbed on the surfaces of solid carriers uniformly. It is preferredthat the diameter of the granules is within the range of about 0.2 to1.5 mm.

In the case of an emulsifiable concentrate, the formulate containsactive ingredient compounds usually in the range of about 5 to 30% byweight, and, in addition, about 5 to 20% by weight of emulsifiers, withthe remainder being liquid carriers. If necessary, spreading agents andanticorrosive agents may be added thereto.

In the case of a flowable composition, the formulate contains activeingredient compounds usually in the range of about 5 to 50% by weight,and, in addition, about 3 to 10% by weight of dispersion wetting agents,with the remainder being water. If necessary, protective colloid agents,preservatives, defoaming agents, etc. may be added thereto.

The compounds of the present invention may be used as herbicides as theyare or in any of the forms of formulation, i.e. the compositions,described above. Thus, the present compounds may be used to control thegrowth of weeds by applying them, in herbicidally effective amounts, tothe weeds or to the locus in which they grow.

The herbicides of the present invention may be applied in effectiveamounts to various lands to be protected, for example, farming landssuch as paddy fields and upland fields, or non-farming lands, prior togermination of weeds or to the weeds in various stages frompre-germination to growing stage.

The dose is generally, expressed as amount of active ingredients, in therange of from about 0.1 to about 10,000 g/ha, preferably from about 1 toabout 5,000 g/ha. The application doses may be varied properly dependingupon the species of weeds being targeted and their growth stages,application sites, weather, etc.

Next, several embodiments of the preparation of the compounds of thisinvention will be explained in detail in the synthetic Examples whichfollow. These Examples are given for the purpose of illustration onlyand are not to be construed as limiting the invention in any way.

EXAMPLE 1 Preparation of6-acetyloxymethyl-2,2-dimethyl-5-phenyl-2H,4H-1,3-dioxin-4-one (CompoundNo. 241)

A mixture of 5-phenyl-2,2,6-trimethyl-2H,4H-1,3-dioxin-4-one (11.0 g),N-succinamide bromide (9.9 g) and 2,2'-azobis(isobutyronitrile) (0.25 g)was suspended in carbon tetrachloride (250 ml), and was allowed to keepstirring for 30 minutes with lighting (tungsten lamp, 300 W). Thereaction mixture was cooled, filtered, and dried by evaporating thesolvent. The crude product was recrystallized from hexane/isopropylether to afford6-bromomethyl-2,2-dimethyl-5-phenyl-2H,4H-1,3-dioxin-4-one (14.59 g,yield 97%).

Then, this product (7.05 g) and sodium acetate (3.9 g) were suspended indimethylformamide (45 ml), and allowed to react with stirring at 70° C.for 2 hours. The reaction mixture was poured into water, and the productwas extracted with ethyl acetate. The organic layer was rinsed withsaturated saline solution and dried with magnesium sulfate, and thesolvent was evaporated. The crude product was purified by silica gelchromatography to afford the captioned compound (5.28 g, yield 81%).

EXAMPLE 2 Preparation of6-acetyloxymethyl-3-(1-methyl-1-phenylethyl)-5-phenyl-2,3-dihydro-4H-1,3-oxazin-4-one(Compound No. 66) (Method A)

A mixture of6-acetyloxymethyl-2,2-dimethyl-5-phenyl-2H,4H-1,3-dioxin-4-one (CompoundNo. 241, 5.0 g) and N-methylene-1-methyl-1-phenylethylamine (2.9 g) wasdissolved in xylene (40 ml) and allowed to react by refluxing for 30minutes. The reaction mixture was purified by silica gel chromatographyto afford the captioned compound (yield 72%).

EXAMPLE 3 Preparation of6-hydroxymethyl-3-(1-methyl-1-phenylethyl)-5-phenyl-2,3-dihydro-4H-1,3-oxazin-4-one(Compound No. 53)

6-Acetyloxymethyl-3-(1-methyl-1-phenylethyl)-5-phenyl-2,3-dihydro-4H-1,3-oxazin-4-one(Compound No. 66, 4.99 g) was dissolved in methanol (55 ml), and anaqueous solution (14 ml) of potassium carbonate (1.3 g) was added slowlythereto. This mixture was allowed to react by stirring at roomtemperature for one hour. Methanol was removed by evaporation, and theresidue was acidified with 2N hydrochloric acid, and extracted withethyl acetate. The organic layer was rinsed with saturated salinesolution, and dried with magnesium sulfate to afford the captionedproduct (4.0 g, yield 91%).

EXAMPLE 4 Preparation of6-methoxymethyl-3-(1-methyl-1-phenylethyl)-5-phenyl-2,3-dihydro-4H-1,3-oxazin-4-one(Compound No. 114)

Sodium hydride (60% in oil, 0.11 g) was suspended in diformaldahyde (2ml), cooled with ice; then a dimethylformamide solution (6 ml) of6-hydroxymethyl-3-(1-methyl-1-phenylethyl)-5-phenyl-2,3-dihydro-4H-1,3-oxazin-4-one(Compound No. 53, 0.8 g) was added slowly thereto. After stirring themixture, methyl iodide (0.71 g) was added, and the mixture was stirredagain at room temperature. The reaction mixture was poured into water,and extracted with ethyl acetate. The organic layer was rinsed withsaturated saline solution, and dried with magnesium sulfate, and thesolvent was evaporated. The crude product was purified by silica gelchromatography to afford the captioned compound (0.56 g, yield 67%).

EXAMPLE 5 Preparation of6-formyl-3-(1-methyl-1-phenylethyl)-5-phenyl-2,3-dihydro-4H-1,3-oxazin-4-one(Compound No. 121)

Pyridinium chlorochromate (4.70 g) was suspended in dichloromethane (20ml), and a dichloromethane solution (27 ml) of6-hydroxymethyl-3-(1-methyl-1-phenylethyl)-5-phenyl-2,3-dihydro-4H-1,3-oxazin-4-one(Compound No. 53, 4.70 g) was added thereto at room temperature. Afterstirring for about 9 hours, a large amount of ether was added andseparated by decantation. The organic layer was dried with magnesiumsulfate and the solvent was evaporated. The crude product was purifiedby silica gel chromatography to afford the captioned compound (4.47 g,yield 96%).

EXAMPLE 6 Preparation of6-Difluoromethyl-3-(1-methyl-1-phenylethyl)-5-phenyl-2,3-dihydro-4H-1,3-oxazin-4-one(Compound No. 34)

Diethylaminosulfate trifluoride (0.51 g) was dissolved indichloromethane (2 ml); then, a dichloromethane solution (5 ml) of6-formyl-3-(1-methyl-1-phenylethyl)-5-phenyl-2,3-dihydro-4H-1,3-oxazin-4-one(Compound No. 121, 1.0 g) was added dropwise at room temperature, andthe mixture was allowed to react, with stirring. The solvent was removedby evaporation, and the captioned compound was obtained by purificationusing silica gel chromatography (0.70 g, yield 66%).

EXAMPLE 7 Preparation of6-Hydroxyiminomethyl-3-(1-methyl-1-phenylethyl)-5-phenyl-2,3-dihydro-4H-1,3-oxazin-4-one(Compound No. 134)

6-Formyl-3-(1-methyl-1-phenylethyl)-5-phenyl-2,3-dihydro-4H-1,3-oxazin-4-one(Compound No. 121, 2.87 g) was dissolved in ethanol (30 ml), and anaqueous solution (15 ml) of hydroxylamine hydrochloric acid (0.65 g) andsodium acetate (1.30 g) was added slowly thereto at room temperature.After stirring for one hour, ethanol was removed by evaporation, andfiltered after adding water. The solid product obtained was rinsed withwater and dried to afford the captioned compound (2.59 g, yield 86%).

EXAMPLE 8 Preparation of 6-Acetyloxymethyl-3-1-methyl-1-(3,5-dichlorophenyl)ethyl!-5-phenyl-2,3-dihydro-4H-1,3-oxazin-4-one(Compound No. 69)

6-Acetyloxymethyl-2,2-dimethyl-5-phenyl-2H, 4H-1,3 -dioxin-4-one(Compound No. 241, 17.1 g) was mixed withN-ethylene-1-methyl-1-(3,5-dichlorophenyl)ethylamine (14.7 g), andxylene (120 ml) was added thereto. After refluxing for one hour, thesolvent was removed by evaporation, and the crude product wasrecrystallized from a mixture of hexane and ethyl acetate to afford thecaptioned compound (22.83 g, yield 85%).

Preparation of 6-Fluoromethyl-3-1-methyl-1-(3,5-dichlorophenyl)ethyl!-5-phenyl-2,3-dihydro-4H-1,3-oxazin-4-one(Compound No. 4)

Diethylaminosulfate trifluoride (0.60 g) was dissolved indichloromethane (3 ml), and a dichloromethane solution (7 ml) of6-hydroxymethyl-3-1-methyl-1-(3,5-dichlorophenyl)ethyl!-5-phenyl-2,3-dihydro-4H-1,3-oxazin-4-one(Compound No. 55, 1.40 g) was added dropwise at -63° C.

After warming to room temperature by stirring for 30 minutes, thereaction mixture was fractionated, and the organic layer was rinsed withwater and dried with magnesium sulfate. The solvent was removed byevaporation, and the crude product was purified by silica gelchromatography to afford the captioned compound (0.99 g, yield 70%).

Preparation of 6-Acetyloxyiminomethyl-3-1-methyl-1-(3,5-dichlorophenyl)ethyl!-5-phenyl-2, 3-dihydro-4H-1,3-oxazin-4-one (Compound No. 147)

A mixture of 6-hydroxyiminomethyl-3-1-methyl-1-(3,5-dichlorophenyl)ethyl!-5-phenyl-2,3-dihydro-4H-1,3-oxazin-4-one(Compound No. 135, 0.60 g) and anhydrous acetic acid (2 ml) was stirredat room temperature for 4 hours. The reaction mixture was poured intowater, and extracted with ethyl acetate. The organic layer was rinsedwith saturated saline solution, and dried with magnesium sulfate. Thesolvent was removed by evaporation, and the crude product was purifiedby silica gel chromatography to afford the captioned compound (0.54 g,yield 94%).

Preparation of 6-Cyano-3-1-methyl-1-(3,5-dichlorophenyl)ethyl!-5-phenyl-2,3-dihydro-4H-1,3-oxazin-4-one(Compound No. 167)

6-Hydroxyiminomethyl-3-1-methyl-1-(3,5-dichlorophenyl)ethyl!-5-phenyl-2,3-dihydro-4H-1,3-oxazin-4-one(Compound No. 135, 0.50 g), triphenylphosphine (0.33 g), carbontetrachloride (0.19 g) and triethylamine (0.13 g) were mixed, anddichloromethane (5 ml) was added thereto. The mixture was refluxed fortwo and one-half hours. The reaction mixture was rinsed with water anddried with magnesium sulfate, then the solvent was removed byevaporation and the crude product was purified by silica gelchromatography to afford the captioned compound (0.39 g, yield 82%).

Preparation of 6-Trifluoromethyl-3-1-methyl-1-(3,5-dichlorophenyl)ethyl!-5-phenyl-2,3-dihydro-4H-1,3-oxazin-4-one(Compound No. 49) (Method B)

Ethyl 2-trifluoroacetyl-2-phenylacetate (1.30 g) andN-methylene-1-methyl-1-(3,5-dichlorophenyl)ethylamine (1.19 g) weremixed, and xylene (10 ml) was added thereto. The mixture was allowed toreact by refluxing for 30 minutes. The solvent was removed byevaporation, and the crude product was recrystallized from a mixture ofhexane and ethyl acetate to afford the captioned compound (1.80 g, yield84%).

Preparation of6-Hydroxymethyl-2,2-dimethyl-5-phenyl-2H,4H-1,3-dioxin-4-one (CompoundNo. 236)

6-Acetyloxymethyl-2,2-dimethyl-5-phenyl-2H,4H-1,3-dioxin-4-one (CompoundNo. 241, 7.46 g) was dissolved in methanol (108 ml), and cooled withice; then, an aqueous solution (27 ml) of potassium carbonate (2.42 g)was added slowly thereto.

After stirring for 30 minutes, methanol was removed by evaporation, theresidue was acidified with 2N hydrochloric acid and the mixture wasfiltered. The crude product was recrystallized from a mixture of hexaneand ethyl acetate to afford the captioned compound (3.84 g, yield 61%).

Preparation of 6-Formyl-2,2-dimethyl-5-phenyl-2H,4H-1,3-dioxin-4-one(Compound No. 246)

Pyridinium chlorochromate (1.29 g) was suspended into dichloromethane (8ml), then a dichloromethane suspension (3 ml) of6-hydroxymethyl-2,2-dimethyl-5-phenyl-2H,4H-1,3-dioxin-4-one (CompoundNo. 236, 0.70 g) was added thereto at room temperature. After stirringfor 5 hours, a large amount of ether was added and extracted bydecantation. The organic layer was dried with magnesium sulfate, thesolvent was removed by evaporation, and the crude product was purifiedby silica gel chromatography to afford the captioned compound (0.43 g,yield 67%).

The melting points and δ-values of H-NMR of the compounds prepared inthe preceding Examples and the compounds prepared by similar preparationmethods are shown in Table 3 below.

                  TABLE 3                                                         ______________________________________                                        Compd.            Solvent CDCl.sub.3                                                                            Melting Point                               No.   .sup.1 H-NMR δ (ppm)                                                                TMS = 0 ppm     (°C.)                                ______________________________________                                        1     1.84 (s, 6H), 4.81 (d, 2H), 5.18 (s, 2H),                                                             82.4-85.0                                             7.23-7.44 (m, 10H)                                                      4     1.75 (s, 6H), 4.84 (d, 2H), 5.37 (s, 2H),                                                             96.1-99.5                                             7.20-7.38 (m, 8H)                                                       34    1.84 (s, 6H), 5.24 (s, 2H), 6.01 (t, 1H),                                                             78.3-80.3                                             7.22-7.43 (m, 10H)                                                      36    1.76 (s, 6H), 5.43 (s, 2H), 6.03 (t, 1H),                                                             112.5-115.8                                           7.20-7.39 (m, 8H)                                                       48    1.85 (s, 6H), 5.21 (s, 2H), 7.23-7.43 (m, 10H)                                                        Oily Substance                                  49    1.76 (s, 6H), 5.42 (s, 2H), 7.20-7.25 (m, 5H),                                                        121.6-123.9                                           7.32-7.38 (m, 3H)                                                       53    1.84 (s, 6H), 4.17 (d, 2H), 5.15 (s, 2H)                                                              156.5-159.5                                           7.21-7.44 (m, 10H)                                                      55    1.74 (s, 6H), 4.19 (s, 2H), 5.34 (s, 2H),                                                             132.4-136.7                                           7.19-7.36 (m, 8H)                                                       66    1.83 (s, 6H), 2.03 (s, 3H), 4.61 (s, 2H), 5.14                                                        Oily Substance                                        (s, 2H), 7.21-7.43 (m, 10H)                                             69    1.74 (s, 6H), 3.33 (s, 3H), 3.98 (s, 2H), 5.35                                                        115.0-117.0                                           (s, 2H), 7.19-7.36 (m, 8H)                                              114   1.83 (s, 6H), 3.30 (s, 3H), 3.95 (s, 2H), 5.17                                                        Oily Substance                                        (s, 2H), 7.20-7.43 (m, 10H)                                             116   1.74 (s, 6H), 3.33 (s, 3H), 3.98 (s, 2H), 5.36                                                        Oily Substance                                        (s, 2H), 7.20-7.36 (m, 8H)                                              121   1.85 (s, 6H), 5.23 (s, 2H), 7.22-7.46 (m, 10H),                                                       94.0-97.7                                             9.36 (s, 1H)                                                            122   1.77 (s, 6H), 5.40 (s, 2H), 7.22 (s, 3H), 7.41                                                         98.9-102.0                                           (s, 5H), 9.38 (s, 1H)                                                   134   1.85 (s, 6H), 5.23 (s, 2H), 7.21-7.43 (m, 10H),                                                       176.0-181.5                                           7.55 (s, 1H), 8.06 (s, 1H)                                                                            (decomposed)                                    135   1.76 (s, 6H), 5.41 (s, 2H), 7.20-7.38 (m, 8H),                                                        187.0-197.0                                           7.57 (s, 1H), 8.15 (s, 1H)                                                                            (decomposed)                                    147   1.76 (s, 6H), 2.16 (s, 3H), 5.45 (s, 2H),                                                             177.7-180.0                                           7.20-7.40 (m, 8H), 7.78 (s, 1H)                                         160   1.75 (s, 6H), 4.00 (s, 3H), 5.43 (s, 2H),                                                             129.5-132.5                                           7.20-7.35 (m, 8H), 7.51 (s, 1H)                                         164   1.84 (s, 6H), 5.20 (s, 2H), 7.26-7.47 (m, 10H)                                                        141.5-145.2                                     167   1.76 (s, 6H), 5.38 (s, 2H), 7.22 (s, 3H),                                                             123.3-127.5                                           7.41 (s, 5H)                                                            236   1.82 (s, 6H), 1.89 (t, 1H), 4.20 (d, 2H),                                                             94.0-96.5                                             7.28-7.43 (m, 5H)                                                       241   1.79 (s, 6H), 2.05 (s, 3H), 4.62 (s, 2H),                                                             Oily Substance                                        7.25-7.42 (m, 5H)                                                       246   1.84 (s, 6H), 7.40-7.50 (m, 5H), 9.46 (s, 1H)                                                         78.0-80.8                                       ______________________________________                                    

Several representative herbicidal compositions using the compounds ofthis invention are shown below. In these formulations, all "parts" areby weight.

FORMULATION EXAMPLE 1 (Emulsifiable Concentrate)

    ______________________________________                                        Compound No. 147        20    parts                                           Xylene                  50    parts                                           Cyclohexane             20    parts                                           Calcium dodecylbenzenesulfonate                                                                       5     parts                                           Polyoxyethylenestyrylphenyl ether                                                                     5     parts                                           ______________________________________                                    

The above substances were mixed and dissolved uniformly to obtain 100parts of an emulsifiable concentrate formulate.

FORMULATION EXAMPLE 2 (Wettable Powder)

    ______________________________________                                        Compound No. 147          20    parts                                         Clay                      70    parts                                         Calcium ligninsulfonate   7     parts                                         Condensate of alkylnaphthalenesulfonic acid                                                             3     parts                                         and formaldehyde                                                              ______________________________________                                    

The above substances were mixed and pulverized using a jet mill toobtain 100 parts of a wettable powder formulate.

FORMULATION EXAMPLE 3 (Flowable)

    ______________________________________                                        Compound No. 147        20     parts                                          Sodium di-(2-ethylhexyl)sulfosuccinate                                                                2      parts                                          Polyoxyethylene nonylphenyl ether                                                                     0.5    parts                                          Defoaming agent         5      parts                                          Propylene glyeol        5      parts                                          Water                   70.5   parts                                          ______________________________________                                    

The above substances were mixed and pulverized uniformly using a wetball mill to obtain 100 parts of a flowable formulate.

The herbicidal effects of the compounds of the present invention areillustrated by the following test examples.

TEST EXAMPLE 1 (Paddy Field Soil Treatment)

Suitable amounts of water and chemical fertilizer were added to paddyfield soil. This soil was filled into 130 cm² plastic pots, followed bykneading to convert it to the state of a paddy field, to which a stockof paddy field rice plant (variety: Koshihikari) composing a pair of twoseedlings, that had been grown in advance in a greenhouse to a stage oftwo leaves, were transplanted to each pot in a population of one stockper pot. Further, in each pot, there were added predetermined amounts ofseeds of Nobie (Echinochloa orizicola), Konagi (Monochoria vaginalisvar. plantaginea), Azena (Lindernia procumbens) and Hotarui (Scirpusjuncoides var. hotarui), respectively, and water was added to a depth of3 cm. On the next day, wettable powder formulates were prepared by themethod described in Formulation Example 2, and diluted with a suitableamount of water up to a concentration of active ingredient of 5 kg or 1kg per ha. The diluted formulate was applied by dropping with a pipette.

After 21 days from the application of the chemicals, the herbicidaleffects on each weed and the phytotoxicity on the paddy field riceplants were assessed according to the following criteria. The resultswhich were obtained are shown in Table 4.

    ______________________________________                                        Evaluation criteria (11 ranks)                                                         Herbicidal effects:                                                                         Phytotoxicity to crop:                                          Ratio of killed weeds                                                                       Ratio of injured plants                                         compared to the                                                                             compared to the                                        Score    control (%)   control (%)                                            ______________________________________                                        0        0             Same as the left column                                1        Above 0 to 10                                                        2        Above 10 to 20                                                       3        Above 20 to 30                                                       4        Above 30 to 40                                                       5        Above 40 to 50                                                       6        Above 50 to 60                                                       7        Above 60 to 70                                                       8        Above 70 to 80                                                       9        Above 80 to 90                                                       10        Above 90 to 100                                                              (withered)                                                           ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                              Active                        Phyto-                                    Compd.                                                                              ingredient                                                                              Herbicidal effects  toxicity                                  No.   Dose g ai/ha                                                                            Nobie   Konagi                                                                              Azena Hotarui                                                                             Rice plant                          ______________________________________                                        4     1000      10      10    10    10    2                                         5000      10      10    10    10    10                                  34    1000      10      10    10    10    0                                         5000      10      10    10    10    2                                   49    1000      10      10    10    10    0                                         5000      10      10    10    10    0                                   69    1000      10      10    10    10    10                                        5000      10      10    10    10    10                                  147   1000      10      10    10    10    6                                         5000      10      10    10    10    7                                   ______________________________________                                         Note:                                                                         Nobie: Echinochloa orizicola                                                  Konagi: Monochoria vaginalis var. plantaginea                                 Azena: Lindernia procumbens                                                   Hotarui: Scirpus juncoides var. hotarui                                  

TEST EXAMPLE 2 (Paddy Field Foliar Application)

Paddy field soil was filled into 130 cm² plastic pots, and suitableamounts of water and chemical fertilizers were added thereto, andkneaded to convert it to the state of a paddy field. A stock of paddyfield rice plant (variety: Koshihikari) composing a pair of twoseedlings, that had been grown in advance in a greenhouse to a stage oftwo leaves, were transplanted into each pot in a population of one stockper pot. Further, in each pot, there were sown predetermined amounts ofseeds of Nobie (Echinochloa orizicola), Konagi (Monochoria vaginalisvar. plantaginea), Azena (Lindernia procumbens) and Hotarui (Scirpusjuncoides var. hotarui), respectively, and water was added to a depth of3 cm.

After having grown the plants in a greenhouse until Nobie (Echinochloaorizicola) reached a stage of 1.5 leaves, wettable powder formulateswere prepared by the method described in Formulation Example 2, anddiluted with a suitable amount of water up to a concentration of theactive ingredient of 5 kg or 1 kg per ha. The diluted formulate wasapplied by dropping with a pipette.

After 21 days from the application of the chemicals, herbicidal effectson each weed and phytotoxicity on paddy field rice plants were assessedbased on the criteria as described in the Test Example 1. The resultsobtained are shown in Table 5.

                  TABLE 5                                                         ______________________________________                                              Active                        Phyto-                                    Compd.                                                                              ingredient                                                                              Herbicidal effects  toxicity                                  No.   Dose g ai/ha                                                                            Nobie   Konagi                                                                              Azena Hotarui                                                                             Rice plant                          ______________________________________                                        4     1000      10      10    10    9     3                                         5000      10      10    10    9     8                                   34    1000      9       9     10    10    0                                         5000      10      10    10    10    0                                   49    1000      10      4     10    10    0                                         5000      10      9     10    10    0                                   69    1000      10      10    10    10    10                                        5000      10      10    10    10    10                                  147   1000      10      10    10    10    3                                         5000      10      10    10    10    8                                   ______________________________________                                         Note:                                                                         Nobie: Echinochloa orizicola                                                  Konagi: Monochoria vaginalis var. plantaginea                                 Azena: Lindernia procumbens                                                   Hotarui: Scirpus juncoides var. hotarui                                  

TEST EXAMPLE 3 (Upland Soil Application)

Upland soil was filled into 130 cm² plastic pots, in which there weresown predetermined amounts of seeds of Nobie (Echinochloa crus-galli),Mehishiba (Digitaria ciliaris) and Enokorogusa (Setaria viridis),respectively, and soil was placed thereon to a thickness of 1 cm.

On the day next to sowing, wettable powder formulates were prepared bythe method described in Formulation Example 2, and diluted with asuitable amount of water up to a concentration of active ingredient of 5kg or 1 kg per ha. The diluted formulate was sprayed uniformly over thesurface of the soil.

After 21 days from the application of the chemicals, herbicidal effectson each weed were assessed based on the criteria described in the TestExample 1. Results obtained are shown in Table 6.

                  TABLE 6                                                         ______________________________________                                        Compd. Active ingredient                                                                         Herbicidal effects                                         No.    Dose g ai/ha                                                                              Nobie    Mehishiba                                                                             Enokorogusa                               ______________________________________                                        4      1000        10       10      9                                                5000        10       10      10                                        34     5000        10       10      10                                        49     5000        8        10      10                                        69     1000        10       10      10                                               5000        10       10      10                                        147    1000        10       10      10                                               5000        10       10      10                                        ______________________________________                                         Note:                                                                         Nobie: Echinochloa crusgalli                                                  Mehishiba: Digitaria ciliaris                                                 Enokorogusa: Setaria viridis                                             

The compounds of the present invention having formula (I) show excellentherbicidal effects at very low doses over a wide range from germinationto growth stage of paddy field annual weeds such as Hie (Echinochloaorizicola), Tamagayatsuri (Cyperus difformis), Konagi (Monochoriavaginalis var. plantaginea), Kikashigusa (Rotala indica var. uliginosa),Azena (Lindernia procumbens), Abunome (Dopatrium junceum) and the like,and paddy field perennial weeds such as Hotarui (Scirpus juncoides var.hotarui), Matsubai (Eleocharis acicularis var longiseta), Heraomodaka(Alisma canaliculatum), Mizugayatsuri (Cyperus serotinus) and the like,and also show high safety for transplanted rice plants and directly sownrice plants in either paddy or upland fields.

In addition, the instant compounds show high herbicidal effects, in soilor on foliar application, on various upland broadleaf weeds such as Tade(Persicaria longiseta), Aobiyu (Amaranthus viridis), Shiroza(Chenopodium album) and the like, annual and perennial Cyperus weedssuch as Hamasuge (Cyperus rotundus), Kihamasuge (Cyperus esculantus),Himekugu (Cyperus brevifolius var. leiolepis), Kayatsurigusa (Cyperusmicroiria), Kogomegayatsuri (Cyperus iria) and the like, and uplandgramineous weeds such as Hie (Echinochloa crus-galli), Mehishiba(Digitaria ciliaris), Enokorogusa (Setaria viridis), Suzumenokatabira(Poa annua), Johnsongrass (Sorghum halepense), Wild oat (Avena sativa),Suzumenoteppo (Alopecurus aequalis var amurensis), and the like, andthey also show characteristically high safety for crops such as soybean,cotton, sugar beet, rape, sunflower, maize, upland rice, wheat and soforth.

The compounds of the present invention can be used not only in paddy andupland fields but also in orchards, mulberry fields, turf, andnon-farming lands. Furthermore, by mixing the compounds of thisinvention with already known compounds, they show complete herbicidaleffects on weeds which are difficult to be controlled by each of thecompounds applied singly, and effectively control various weeds bysynergistic herbicidal effects at doses at which single compound hardlycan control. In addition, the compounds of the present invention showhigh safety for crops such as paddy field rice, soybean, cotton, sugarbeet, rape, sunflower, maize, upland rice, wheat and the like;therefore, they can provide herbicides which are very useful inagriculture.

While the invention has been described in terms of various preferredembodiments, the skilled artisan will appreciate that variousmodifications, substitutions, omissions, and changes may be made withoutdeparting from the spirit thereof. Accordingly, it is intended that thescope of the present invention be limited solely by the scope of thefollowing claims, including equivalents thereof.

What is claimed is:
 1. A compound having the formula: ##STR16## wherein: R¹ is a lower alkyl radical, a lower alkenyl radical, a lower alkynyl radical, an aryl radical which is unsubstituted or substituted, or an aralkyl radical which is unsubstituted or substituted;R² is a lower hydroxyalkyl radical, a lower alkoxyalkyl radical, a lower acyloxyalkyl radical, a formyl radical, a hydroxyiminomethyl radical, a lower alkoxyiminomethyl radical, a lower acyloxyiminomethyl radical, a cyano radical or a lower alkoxycarbonyl radical; R³ is a lower alkyl radical, an aryl radical which is unsubstituted or substituted, or an aralkyl radical which is unsubstituted or substituted; and R⁴ and R⁵, independently, are each a lower alkyl radical; or R⁴ and R⁵, taken together with the carbon atom to which they are bonded, combine to form a 3- to 8-membered carbocyclic ring which is unsubstituted or is substituted by 1 or more lower alkyl radicals.
 2. A method for controlling the growth of weeds at a locus comprising applying to said weeds or to the locus in which they grow a herbicidally effective amount of a compound having the formula: ##STR17## wherein: R¹ is a lower alkyl radical, a lower alkenyl radical, a lower alkynyl radical, an aryl radical which is unsubstituted or substituted, or an aralkyl radical which is unsubstituted or substituted;R² is a lower hydroxyalkyl radical, a lower alkoxyalkyl radical, a lower acyloxyalkyl radical, a formyl radical, a hydroxyiminomethyl radical, a lower alkoxyiminomethyl radical, a lower acyloxyiminomethyl radical, a cyano radical or a lower alkoxycarbonyl radical; R³ is a lower alkyl radical, an aryl radical which is unsubstituted or substituted, or an aralkyl radical which is unsubstituted or substituted; and R⁴ and R⁵, independently, are each a lower alkyl radical; or R⁴ and R⁵, taken together with the carbon atom to which they are bonded, combine to form a 3- to 8-membered carbocyclic ring which is unsubstituted or is substituted by 1 or more lower alkyl radicals.
 3. A compound having the formula: ##STR18## wherein: R¹ is a lower alkyl radical; a lower alkenyl radical; a lower alkynyl radical; an aryl radical which is phenyl or naphthyl, each of which is unsubstituted or is substituted by one or more members selected from the group consisting of halogen, lower alkyl, lower alkoxy, lower haloalkyl, lower haloalkoxy and nitro; or an aralkyl radical wherein the alkyl portion has 1 to 4 carbon atoms, and wherein the aryl portion is phenyl or naphthyl, each of which is unsubstituted or is substituted by one or more members selected from the group consisting of halogen, lower alkyl, lower alkoxy, lower haloalkyl, lower haloalkoxy and nitro;R² is a lower hydroxyalkyl radical, a lower alkoxyalkyl radical, a lower acyloxyalkyl radical, a formyl radical, a hydroxyiminomethyl radical, a lower alkoxyiminomethyl radical, a lower acyloxyiminomethyl radical, a cyano radical or a lower alkoxycarbonyl radical; R³ is a lower alkyl radical; an aryl radical which is phenyl or naphthyl, each of which is unsubstituted or is substituted by one or more members selected from the group consisting of halogen, lower alkyl, lower alkoxy, lower haloalkyl, lower haloalkoxy and nitro; or an aralkyl radical wherein the alkyl portion has 1 to 4 carbon atoms, and wherein the aryl portion is phenyl or naphthyl, each of which is unsubstituted or is substituted by one or more members selected from the group consisting of halogen, lower alkyl, lower alkoxy, lower haloalkyl, lower haloalkoxy and nitro; and R⁴ and R⁵, independently, are each a lower alkyl radical; or R⁴ and R⁵ are taken together with the carbon atom to which they are bonded to form a 3- to 8-membered saturated carbocyclic ring which is unsubstituted or is substituted by 1 or more lower alkyl radicals.
 4. The compound according to claim 3, having the formula: ##STR19## wherein: X is halogen or lower alkyl;Y is halogen or lower haloalkyl; n is 0 or 1; and m is 0, 1 or 2, provided that when m is 2, then the substituents represented by Y can be the same or different.
 5. A method for controlling the growth of weeds at a locus comprising applying to said weeds or to the locus in which they grow a herbicidally effective amount of a compound as claimed in claim
 3. 6. A method for controlling the growth of weeds at a locus comprising applying to said weeds or to the locus in which they grow a herbicidally effective amount of a compound as claimed in claim
 4. 7. A compound having the formula: ##STR20## wherein: R¹ is a lower alkyl radical; a lower alkenyl radical; a lower alkynyl radical; an aryl radical which is phenyl or naphthyl, each of which is unsubstituted or is substituted by one or more members selected from the group consisting of halogen, lower alkyl, lower alkoxy, lower haloalkyl, lower haloalkoxy and nitro; or an aralkyl radical wherein the alkyl portion has 1 to 4 carbon atoms, and wherein the aryl portion is phenyl or naphthyl, each of which is unsubstituted or is substituted by one or more members selected from the group consisting of halogen, lower alkyl, lower alkoxy, lower haloalkyl, lower haloalkoxy and nitro;R² is a formyl radical, a hydroxyiminomethyl radical, a lower alkoxyiminomethyl radical, a lower acyloxyiminomethyl radical, a cyano radical or a lower alkoxycarbonyl radical; R³ is a lower alkyl radical; an aryl radical which is phenyl or naphthyl, each of which is unsubstituted or is substituted by one or more members selected from the group consisting of halogen, lower alkyl, lower alkoxy, lower haloalkyl, lower haloalkoxy and nitro; or an aralkyl radical wherein the alkyl portion has 1 to 4 carbon atoms, and wherein the aryl portion is phenyl or naphthyl, each of which is unsubstituted or is substituted by one or more members selected from the group consisting of halogen, lower alkyl, lower alkoxy, lower haloalkyl, lower haloalkoxy and nitro; and R⁴ and R⁵, independently, are each a lower alkyl radical; or R⁴ and R⁵ are taken together with the carbon atom to which they are bonded to form a 3- to 8-membered saturated carbocyclic ring which is unsubstituted or is substituted by 1 or more lower alkyl radicals.
 8. The compound according to claim 7, having the formula: ##STR21## wherein: X is halogen or lower alkyl;Y is halogen or lower haloalkyl; n is 0 or 1; and m is 0, 1 or 2, provided that when m is 2, then the substituents represented by Y can be the same or different.
 9. A method for controlling the growth of weeds at a locus comprising applying to said weeds or to the locus in which they grow a herbicidally effective amount of a compound as claimed in claim
 7. 10. A method for controlling the growth of weeds at a locus comprising applying to said weeds or to the locus in which they grow a herbicidally effective amount of a compound as claimed in claim
 8. 11. A method for controlling the growth of weeds at a crop locus without substantial damage to the crop which is grown at said locus, said method comprising applying to said weeds or to said locus a compound having the formula: ##STR22## wherein: R¹ is a lower alkenyl radical, a lower alkynyl radical, an aryl radical which is unsubstituted or substituted, or an aralkyl radical which is unsubstituted or substituted;R² is a lower hydroxyalkyl radical, a lower alkoxyalkyl radical, a lower acyloxyalkyl radical, a formyl radical, a hydroxyiminomethyl radical, a lower alkoxyiminomethyl radical, a lower acyloxyiminomethyl radical, a cyano radical or a lower alkoxycarbonyl radical; R³ is a lower alkyl radical, an aryl radical which is unsubstituted or substituted, or an aralkyl radical which is unsubstituted or substituted; and R⁴ and R⁵, independently, are each a lower alkyl radical; or R⁴ and R⁵, taken together with the carbon atom to which they are bonded, combine to form a 3- to 8-membered carbocyclic ring which is unsubstituted or is substituted by 1 or more lower alkyl radicals; in an amount which is herbicidally effective and which is non-phytotoxic to the crop.
 12. The method according to claim 11, wherein, in the compound of formula (I):R¹ is a lower alkyl radical; a lower alkenyl radical; a lower alkynyl radical; an aryl radical which is phenyl or naphthyl, each of which is unsubstituted or is substituted by one or more members selected from the group consisting of halogen, lower alkyl, lower alkoxy, lower haloalkyl, lower haloalkoxy and nitro; or an aralkyl radical wherein the alkyl portion has 1 to 4 carbon atoms, and wherein the aryl portion is phenyl or naphthyl, each of which is unsubstituted or is substituted by one or more members selected from the group consisting of halogen, lower alkyl, lower alkoxy, lower haloalkyl, lower haloalkoxy and nitro; R² is a lower alkoxyalkyl radical, a lower acyloxyalkyl radical, a formyl radical, a hydroxyiminomethyl radical, a lower alkoxyiminomethyl radical, a lower acyloxyiminomethyl radical, a cyano radical or a lower alkoxycarbonyl radical; R³ is a lower alkyl radical; an aryl radical which is phenyl or naphthyl, each of which is unsubstituted or is substituted by one or more members selected from the group consisting of halogen, lower alkyl, lower alkoxy, lower haloalkyl, lower haloalkoxy and nitro; or an aralkyl radical wherein the alkyl portion has 1 to 4 carbon atoms, and wherein the aryl portion is phenyl or naphthyl, each of which is unsubstituted or is substituted by one or more members selected from the group consisting of halogen, lower alkyl, lower alkoxy, lower haloalkyl, lower haloalkoxy and nitro; and R⁴ and R⁵, independently, are each a lower alkyl radical; or R⁴ and R⁵ are taken together with the carbon atom to which they are bonded to form a 3- to 8-membered saturated carbocyclic ring which is unsubstituted or is substituted by 1 or more lower alkyl radicals.
 13. The method according to claim 12, wherein the compound of formula (I) has the formula: ##STR23## wherein: X is halogen or lower alkyl;Y is halogen or lower haloalkyl; n is 0 or 1; and m is 0, 1 or 2, provided that when m is 2, then the substituents represented by Y can be the same or different.
 14. The method according to claim 11, wherein said crop locus comprises a rice paddy field or an upland rice field.
 15. The compound according to claim 3, wherein R¹ is a branched lower alkyl radical.
 16. The compound according to claim 15, wherein R¹ is branched alkyl having 3 or 4 carbon atoms.
 17. The compound according to claim 16, wherein R¹ is isobutyl or isopropyl.
 18. The compound according to claim 3, wherein R¹ is phenyl or phenyl substituted by halogen or lower alkyl.
 19. The compound according to claim 3, wherein R³ is phenyl or 2-naphthyl, each of which is unsubstituted or is substituted by one or two halogen, lower haloalkyl or lower haloalkoxy.
 20. The compound according to claim 3, wherein R⁴ is methyl.
 21. The compound according to claim 3, wherein R⁵ is methyl.
 22. The compound according to claim 3, wherein:R¹ is C₃ -C₄ branched alkyl, phenyl, or phenyl substituted by halogen or lower alkyl; R³ is phenyl or 2-naphthyl, each of which is unsubstituted or is substituted by one or two halogen, lower haloalkyl or lower haloalkoxy; R⁴ is methyl; and R⁵ is methyl.
 23. The compound according to claim 8, which is 6-acetyloxyiminomethyl-3- 1-methyl-1-(3,5-dichlorophenyl)ethyl!-5-phenyl-2,3-dihydro-4H-1,3-oxazin-4-one.
 24. A herbicidal composition comprising a herbicidally effective amount of a compound of formula (I) as claimed in claim 1 and an agriculturally acceptable inert carrier.
 25. A herbicidal composition comprising a herbicidally effective amount of a compound of formula (I) as claimed in claim 3 and an agriculturally acceptable inert carrier.
 26. A herbicidal composition comprising a herbicidally effective amount of a compound of formula (I) as claimed in claim 22 and an agriculturally acceptable inert carrier.
 27. A herbicidal composition comprising a herbicidally effective amount of a compound of formula (I-1) as claimed in claim 4 and an agriculturally acceptable inert carrier.
 28. The composition according to claim 24, comprising from about 0.1 to about 99% by weight of compound of formula (I).
 29. The composition according to claim 28, comprising from about 1 to about 80% by weight of compound of formula (I).
 30. The composition according to claim 28, which is a wettable powder comprising from about 25 to about 90% by weight of compound of formula (I), the remainder of the composition consisting of one or more solid carriers and one or more dispersion wetting agents.
 31. The composition according to claim 29, which is a granule comprising from about 1 to about 35% by weight of compound of formula (I), the remainder of the composition consisting of one or more solid carriers and one or more surfactants.
 32. The composition according to claim 29, which is an emulsifiable concentrate comprising from about 5 to about 30% by weight of compound of formula (I) and from about 5 to about 20% by weight of one or more emulsifiers, the remainder of the composition consisting of one or more solid carriers.
 33. The composition according to claim 29, which is a flowable comprising from about 5 to about 50% by weight of compound of formula (I) and from about 3 to about 10% by weight of one or more dispersion wetting agents, the remainder of the composition consisting of water.
 34. The method according to claim 5, wherein, in the compound of formula (I):R¹ is C₃ -C₄ branched alkyl, phenyl, or phenyl substituted by halogen or lower alkyl; R³ is phenyl or 2-naphthyl, each of which is unsubstituted or is substituted by one or two halogen, lower haloalkyl or lower haloalkoxy; R⁴ is methyl; and R⁵ is methyl.
 35. The method according to claim 34, wherein the compound of formula (I) has the formula: ##STR24## wherein: X is halogen or lower alkyl;Y is halogen or lower haloalkyl; n is 0 or 1; and m is 0, 1 or 2, provided that when m is 2, then the substituents represented by Y can be the same or different.
 36. A method for controlling the growth of weeds at a locus comprising applying to said weeds or to the locus in which they grow a herbicidally effective amount of a composition as claimed in claim
 24. 37. The method according to claim 2, wherein the locus to which said compound is applied is farming land.
 38. The method according to claim 37, wherein said farming land comprises paddy fields or upland fields.
 39. The method according to claim 2, wherein the locus to which said compound is applied is non-farming land.
 40. The method according to claim 2, wherein said compound is applied to said locus prior to germination of weeds.
 41. The method according to claim 2, wherein said compound is applied to said weeds or the locus in which they grow at a stage of growth from pre-germination to growing.
 42. The method according to claim 2, wherein said compound is applied at a rate of between about 0.1 and about 10,000 g/ha.
 43. The method according to claim 42, wherein said compound is applied at a rate of between about 1 and about 5,000 g/ha.
 44. The method according to claim 2, wherein said compound is applied to a crop-growing area in which the crop which has been planted or which is to be planted is paddy field rice, soybean, cotton, sugar beet, rape, sunflower, maize, upland rice or wheat.
 45. The method according to claim 2, wherein said compound is applied to orchards, mulberry fields, turf or non-farming land.
 46. A compound having the formula: ##STR25## wherein: R⁶ is an aryl radical which is unsubstituted or is substituted; andR⁷ is hydroxymethyl, acetyloxymethyl or formyl.
 47. The compound according to claim 46 wherein R⁶ is an aryl radical which is phenyl or naphthyl, each of which is unsubstituted or is substituted by one or more members selected from the group consisting of halogen, lower alkyl, lower alkoxy, lower haloalkyl, lower haloalkoxy and nitro.
 48. A process for the preparation of a compound as claimed in claim 1, said process comprising reacting a compound of the formula ##STR26## with a compound of the formula ##STR27##
 49. The process according to claim 48, wherein the reactants are employed in the amount of from about 0.5 to about 2 moles of compound of formula (III) per mole of compound of formula (II') or (IV).
 50. The process according to claim 49, wherein the reactants are employed in the amount of from about 0.9 to abut 1.1 moles of compound of formula (III) per mole of compound of formula (II') or (IV).
 51. A process for the preparation of a compound of formula (I) as claimed in claim 43 wherein R² is hydroxymethyl, lower alkoxymethyl, formyl, hydroximinomethyl, lower alkoxyiminomethyl, lower acyloxyiminomethyl or cyano, said process comprising:(a) converting a compound of formula (I) wherein R² is acetyloxymethyl to the corresponding compound of formula (I) wherein R² is hydroxymethyl; (b) converting a compound of formula (I) wherein R² is hydroxymethyl to the corresponding compound of formula (I) wherein R² is lower alkoxymethyl; (c) converting a compound of formula (I) wherein R² is hydroxymethyl to the corresponding compound of formula (I) wherein R² is formyl; (d) converting a compound of formula (I) wherein R² is formyl to the corresponding compound of formula (I) wherein R² is hydroxyiminomethyl; (e) converting a compound of formula (I) wherein R² is hydroxyiminomethyl to the corresponding compound of formula (I) wherein R² is lower alkoxyiminomethyl; (f) converting a compound of formula (I) wherein R² is hydroxyiminomethyl to the corresponding compound of formula (I) wherein R² is lower acyloxyiminomethyl; or (g) converting a compound of formula (I) wherein R² is hydroxyiminomethyl to the corresponding compound of formula (I) wherein R² is cyano. 